Download NA/400 - NICNAS

File No: NA/400
Date: May 1996
NATIONAL INDUSTRIAL CHEMICALS NOTIFICATION
AND ASSESSMENT SCHEME
FULL PUBLIC REPORT
Polymer E94156
This Assessment has been compiled in accordance with the provisions of the Industrial
Chemicals (Notification and Assessment) Act 1989 (the Act), and Regulations. This
legislation is an Act of the Commonwealth of Australia. The National Industrial Chemicals
Notification and Assessment Scheme (NICNAS) is administered by Worksafe Australia
which also conducts the occupational health & safety assessment. The assessment of
environmental hazard is conducted by the Department of the Environment, Sport, and
Territories and the assessment of public health is conducted by the Department of Health
and Family Services
For the purposes of subsection 78(1) of the Act, copies of this full public report may be
inspected by the public at the Library, Worksafe Australia, 92-94 Parramatta Road,
Camperdown NSW 2050, between the hours of 10.00 a.m. and 12.00 noon and 2.00 p.m.
and 4.00 p.m. each week day except on public holidays.
For Enquiries please contact the Administration Coordinator at:
Street Address: 92 Parramatta Rd Camperdown, NSW 2050, AUSTRALIA
Postal Address: GPO Box 58, Sydney 2001, AUSTRALIA
Telephone: (61) (02) 577-9466 FAX (61) (02) 577-9465
Director
Chemicals Notification and Assessment
NA/400
FULL PUBLIC REPORT
Polymer E94156
1.
APPLICANT
Coates Brothers Australia Pty Limited of 323 Chisholm Road AUBURN NSW 2144
has submitted a limited notification statement in support of their application for an
assessment certificate for Polymer E94156.
2.
IDENTITY OF THE CHEMICAL
Polymer E94156 is not considered to be hazardous based on the nature of the
chemical and the data provided. Therefore the chemical name, CAS number,
molecular and structural formulae, molecular weight, spectral data and details of the
polymer composition have been exempted from publication in the Full Public Report
and the Summary Report.
Other names:
polyether/polyester urethane acrylate
Trade name:
E94156
Number-average
molecular weight:
>1000
Maximum percentage of low
molecular weight species
(molecular weight < 1000):
(molecular weight < 500):
Method of detection
determination:
3.
<5%
<2%
and the notified substance can be detected using GPC
and identified using infrared spectroscopy (IR)
PHYSICAL AND CHEMICAL PROPERTIES
Appearance at 20°C
and 101.3 kPa:
viscous colourless liquid
Melting point:
decomposes at >180°C (at 760 mm Hg)
Specific gravity:
1.16 g/cm3
Vapour pressure:
not stated estimated as negligible
FULL PUBLIC REPORT
2
Water solubility:
not determined
Partition co-efficient
(n-octanol/water):
not determined
Hydrolysis as a function
of pH:
notified polymer has no hydrolysable
functionalities
Adsorption/Desorption:
not determined
Dissociation constant:
notified polymer has no dissociable groups
Flash point:
>100°C
Flammability limits:
not flammable
Autoignition temperature:
not determined
Explosive properties:
not explosive
Reactivity/Stability:
not reactive
Comments on Physico-Chemical Properties
Data on vapour pressure was not supplied, however, the notifier considers that it
would be negligible based on experience with similar chemicals. Water solubility is
likely to be less than 1 ppm based on the notifier’s experience with similar chemicals
and the molecular weight and nature of the notified chemical. No information on
hydrolysis was provided, however, the notified chemical has no hydrolysable
functionalities; similarly the lack of dissociable groups was given as the reason for
the omission of data on the dissociation constant.
Partition coefficient data is not applicable as a polymer of this molecular size
(number-average molecular weight (NAMW) > 1000) with its predicted low solubility,
is not expected to cross biological membranes.
No measurement of
adsorption/desorption was made, although upon drying the notified substance is
expected to adsorb to the soil.
4.
PURITY OF THE CHEMICAL
Degree of purity:
>98%
Toxic or hazardous
impurities:
none known
Impurities:
<1.0%
One of the impurities present is listed as hazardous on the List of Designated
Hazardous Substances (1) although no threshold limits for the classification of a
mixture containing this chemical as hazardous are stated. It is a skin and eye irritant
FULL PUBLIC REPORT
3
in rabbits (2). It is moderately toxic to rats and induced effects in the liver and further
damage to the central nervous system through repeated oral administration (2).
Another of the impurities is not listed as hazardous on the List of Designated
Hazardous Substances (1) however it is a slight eye and skin irritant to rabbits and a
possible skin sensitiser in man (2).
Maximum content
of residual monomers:
<1.0%
Additives/Adjuvants:
none stated
5.
USE, VOLUME AND FORMULATION
The notified polymer will be used as a binder in printing ink formulations. The
notified polymer will be imported at a rate of 1-5 tonnes/year for the first five years.
The notified polymer will be imported in 25kg plastic drums. The notified polymer will
be blended locally into electron beam curable printing inks.
Application of the inks to various substrates is by off-set printing at a limited number
of sites. The substrates to be printed include paper/plastics such as polymer coated
boards for aseptic packages. The cured notified substrate typically represents 1020% of the total ink formulation, but will be diluted by printers, for use, to < 2%.
6.
OCCUPATIONAL EXPOSURE
Exposure during transport and warehousing is unlikely and will only occur due to
accidental release from storage containers. The main areas where employees will
be exposed to the notified polymer will be during the blending operation and during
use of the manufactured printing inks. The notified polymer is pumped into sealed
mixing vessels along with other ink ingredients. The formulation is then milled to
reduce particulates. Milling operations are conducted under local exhaust ventilation
to reduce atmospheric contamination by volatiles released from the ink. The
formulated ink, containing <25% of the notified polymer, is then packaged for
distribution to printers in 10-25 kg drums. Staff involved in blending procedures will
potentially be exposed to the notified polymer for periods of 5-6 hours/day for 50
days/year. During blending and milling procedures, quality control staff will sample
and analyse the product and can thus be exposed to the notified polymer.
The printing inks manufactured using the notified polymer are used in offset printers
and cured using electron beams. The formulations as supplied, containing <25% of
the notified polymer, are diluted prior to use so that the final concentration of the
notified polymer used in printing is <2%. Printers will be exposed during ink
replenishment and during maintenance of the printing equipment. During
maintenance cleaning agents including solvents (short to medium length chain
alcohols) and water based detergents will be used, these could increase exposure
through mobilisation of the notified polymer.
FULL PUBLIC REPORT
4
7.
PUBLIC EXPOSURE
The notified polymer will be formulated by Coates Brothers Australia Pty Ltd into a
printing ink. The printing inks will not be available to the public, and will be used in
commercial printing establishments and applied to plastic/paper bottles. The final
concentration of the notified polymer in the ink used on these items will be <2%. The
public will be exposed to the printing inks once they have been cured on the surface
of product packaging such as shampoo bottles. In such instances the polymer,
which has a NAMW of >1000, will be immobilised in the matrix of the ink and should
pose negligible hazard to the public.
Minor public exposure may result from disposal of unused polymer/printing ink, or
accidental spillage of the notified polymer or formulated printing ink during transport,
formulation and storage. However, adequate measures are described by the notifier
to minimise the risk of public exposure during formulation, disposal, or in the event of
accidental spillage.
8.
ENVIRONMENTAL EXPOSURE
Release
Formulation of the ink products will be in a sealed mixing vessel, with ingredients
pumped into it for use. Milling, to reduce particulates, is conducted under exhaust
ventilation. The notifier indicated that the maximum yearly loss from blending will be
~1-2% or 100 kg. Release to the environment will be through washing of the
blending tanks or spillages arising from blending. Off-specification material will be
electron beam cured and disposed of at approved landfill sites. The proportion of
this material is expected to be 0.1-0.2% of the printing ink formulation.
The possibility exists for spillage of the notified substance to occur upon dilution for
use. Loss of notified substance will also occur during off-set printing. It has been
estimated that these losses will be of the order of 0.5-5%, depending on the nature
of the off-set printer. Environmental exposure during the cleaning of ink from printing
machines is negligible because all washes arising from the printing machines are to
be collected in drums and disposed of at approved liquid waste disposal facilities.
The polymer when cured by an electron beam will bind to the paper or plastic
substrate (mechanism unknown) and be widely distributed with the substrate.
Treatment and disposal of any spillages is adequately dealt with in the Material
Safety Data Sheet (MSDS).
Fate
Residues from washing blending tanks, drums and printing equipment with organic
solvents, such as alcohols or water-based detergents, will be collected in sealed
drums. These residues will be collected for treatment at a licensed liquid waste
disposal facility. The washed drums are returned to Coates for reuse. Disposal of
residues will be according to government regulations.
FULL PUBLIC REPORT
5
As an electron-cured polymer the notified substance is expected to have negligible
interaction with soils and in the event of a minor spill, is of low concern (3). Cured
polymer will share the fate of its substrate.
Recycling is a growing industry in Australia. Waste paper is repulped using a variety
of alkalis, dispersing agents, wetting agents, water emulsifiable organic solvents and
bleaching agents. These chemicals enhance the fibre separation, ink detachment
from the fibres, pulp brightness and the whiteness of the paper. After pulping, the
contaminants and the ink are separated from the fibres by pumping the stock
through various heat washing, screening, cleaning, flotation and dispersion stages.
Similarly, the recycling of plastics will use a variety of physical and chemical
processes.
The notifier has provided no data on the likely behaviour of the polymer during
recycling processes. The hydrolysis of ether/ester linkages under alkaline conditions
will be minimal due to the low solubility of the polymer. The polymer therefore is
likely to survive recycling conditions, either remaining bound to the pulp or becoming
associated with the sludge. In the latter case, the polymer will arrive in landfill where
it can be expected to remain intact, or be destroyed through incineration.
9.
EVALUATION OF TOXICOLOGICAL DATA
The Act does not require the provision of toxicological data for polymers of NAMW
greater than 1,000. However the following studies were supplied by the notifier as
part of the submission.
9.1
Acute Toxicity
Summary of the acute toxicity of Polymer E94156
Test
Species
Outcome
Reference
skin irritation
rabbit
not an irritant
4
eye irritation
rabbit
not an irritant
5
9.1.4 Skin Irritation (4)
Species/strain:
New Zealand White rabbit
Number/sex of animals:
5 female
Observation period:
4 hour application, 72 hours observation
Method of administration:
semi occluded application
FULL PUBLIC REPORT
6
Draize scores (6):
Time after
treatment
(hours)
0
Animal #
1
2
3
4
5
i
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
72
0
0
0
0
0
Erythema
1
72
Oedema
i
See Attachment 1 for Draize scales
Test method:
in accordance with OECD Guidelines for
Testing Chemicals (7)
Result:
non-irritating
9.1.5 Eye Irritation (5)
Species/strain:
New Zealand White rabbit
Number/sex of animals:
3 female
Observation period:
72 hours
Method of administration:
0.1 ml polymer (liquid) conjunctival sac of left
eye of each rabbit
FULL PUBLIC REPORT
7
Draize scores (6) of unirrigated eyes:
Time after instillation
Animal
1 hour
1 day
2 days
3 days
oa
ab
oa
ab
oa
ab
oa
ab
1
i
0
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
0
3
0
0
0
0
0
0
0
0
Cornea
Iris
1
0
0
0
0
2
0
0
0
0
3
0
0
0
0
Conjunctiva
rc
cd
de
rc
cd
de
rc
cd
de
rc
cd
de
1
1
1
1
0
0
0
0
0
0
0
0
0
2
1
1
1
0
0
0
0
0
0
0
0
0
3
1
0
1
0
0
0
0
0
0
0
0
0
i
a
9.4
See Attachment 1 for Draize scales
Opacity b Area c Redness d Chemosis
e
Discharge
Test method:
in accordance with OECD Guidelines for
Testing Chemicals (7)
Result:
slight irritant, not corrosive
Overall Assessment of Toxicological Data
Toxicological data was only provided for skin and eye irritation. In rabbits the notified
polymer was not a skin irritant but was a slight eye irritant, effects were only noted
one hour after application of the test chemical and no effects on the eye were
apparent after 24 hours.
10.
ASSESSMENT OF ENVIRONMENTAL EFFECTS
No ecotoxicological data were provided, which is acceptable for polymers of NAMW
> 1000 according to the Act.
Due to its high NAMW the notified polymer is not expected to cross biological
membranes.
FULL PUBLIC REPORT
8
11.
ASSESSMENT OF ENVIRONMENTAL HAZARD
The polymer is unlikely to present a hazard to the environment at any stage of its
use. It is expected that most of the notified substance will not be released from the
processing/blending sites until it has been electron-cured. The ultimate fate of the
cured polymer on substrate is disposal as land-fill. Leaching of such wastes into the
soil is not expected.
Uncured polymer wastes are expected to be a maximum of 100 kg per year as a
result of washing blending tanks, drums or printing equipment. Residues will be
sealed in drums and treated at liquid waste disposal facilities.
The low level environmental exposure of the polymer as a result of normal use,
together with its expected lack of biological activity, indicate that the overall
environmental hazard should be negligible.
12.
ASSESSMENT OF PUBLIC AND OCCUPATIONAL HEALTH AND SAFETY
EFFECTS
Occupational exposure to the notified polymer is unlikely during transport and
storage. Occupational exposure will mainly occur during blending operations when
the polymer will be milled and blended to make printing ink containing <25% of the
notified polymer. Exposure to this ink will also occur during printing, however the ink
is further diluted with solvents resulting in a concentration of the notified polymer of
<2% in the ink as used. Exposure to the notified polymer will be limited through the
use of equipment and practices taken to minimise exposure to the other components
of the ink such as solvents.
The notified polymer will be incorporated into industrial printing inks which will be
applied to paper/plastics and cured using electron beams. Public exposure to the
notified chemical will result by contact with products to which the printing inks have
been applied. However, the polymer, which has a NAMW of >1000, will be
immobilised in the printing ink after curing, and as such would pose a negligible
public risk. The potential for minor public exposure exists during formulation,
transport and disposal of the printing ink/polymer which is minimised by the
recommended practices during these tasks.
The notified polymer contains low levels of a hazardous impurity and low levels of a
residual monomer, however, these are at levels that are unlikely to render the
notified polymer as hazardous. On the basis of the available toxicity data on skin
and eye irritation in rabbits the notified polymer would not be classified as hazardous
according to the criteria of Worksafe Australia (8), however it produced slight short
term eye irritant effects in the rabbit so there is some potential for eye irritation if
ocular exposure of employees occurs. Eye contact should be avoided.
FULL PUBLIC REPORT
9
13.
RECOMMENDATIONS
To minimise occupational exposure to Polymer E94156 the following guidelines and
precautions should be observed:

if engineering controls and work practices are insufficient to reduce exposure
to Polymer E94156 to a safe level, then the following personal protective
equipment which conforms to Australian Standard (AS) or Australian/New
Zealand Standard (AS/NZS) should be worn;
safety goggles should be selected and fitted in accordance with
AS 1336 (9) to comply with AS/NZS 1337 (10) and eye contact with the
notified polymer and products containing it avoided,
industrial clothing must conform to the specifications detailed in
AS 2919 (11) and AS 3765.1 (12),
impermeable gloves or mittens conforming to AS 2161 (13) and
AS 3765.1 (12),
all occupational footwear should conform to AS/NZS 2210 (14);

spillage of the notified chemical should be avoided, spillages should be
cleaned up promptly with absorbents which should then be put into containers
for disposal;

good personal hygiene should be practised to minimise the potential for
ingestion;

a copy of the MSDS should be easily accessible to employees.
14.
MATERIAL SAFETY DATA SHEET
The MSDS for the notified chemical was provided in accordance with the National
Code of Practice for the Preparation of a Material Safety Data Sheets (15).
This MSDS was provided by Coates Brothers Australia Pty Limited as part of their
notification statement. It is reproduced here as a matter of public record. The
accuracy of this information remains the responsibility of Coates Brothers Australia
Pty Limited.
15.
REQUIREMENTS FOR SECONDARY NOTIFICATION
Under the Act, secondary notification of the notified chemical shall be required if any
of the circumstances stipulated under subsection 64(2) of the Act arise. No other
specific conditions are prescribed.
FULL PUBLIC REPORT
10
16.
REFERENCES
1.
National Occupational Health and Safety Commission, 1994. List of
designated hazardous substances [NOHSC:10005(1994)], AGPS, Canberra,
1994
2.
Toxline Silver Platter (1995). Toxline SilverPlatter CD-ROM database, 1994September 1995, Silver Platter International N.V.
3.
Nabholz J V, Miller P and Zeeman M (1993)
“Environmental Risk
Assessment of New Chemicals Under the Toxic Substances Control Act
(TSCA) Section Five", Environmental Toxicology and Risk Assessment,
ASTM STP 1179, Wayne G. Landis, Jane S. Hughes and Michael A. Lewis,
Eds. American Society for Testing and Minerals, Philadelphia, 1993, p48-49.
4.
Robbins M C (1995). Project Number 3011/1 - An Acute Skin Irritation Study
in the Rabbit with Polyether/polyester Urethane Acrylate E94156, BIBRA
International, Carshalton, Surrey, UK.
5.
Robbins M C (1995). Project Number 3011/2 - An Acute Eye Irritation Study
in the Rabbit with Polyether/polyester Urethane Acrylate E94156, BIBRA
International, Carshalton, Surrey, UK.
6.
Draize, J. H. 1959, ‘Appraisal of the Safety of Chemicals in Foods, Drugs and
Cosmetics’, Association of Food and Drug Officials of the US, 49.
7.
Organisation for Economic Co-operation and Development, OECD Guidelines
for Testing of Chemicals, OECD, Paris, France.
8.
National Occupational Health and Safety Commission 1994, Approved
Criteria for Classifying Hazardous Substances [NOHSC:1008(1994)],
Australian Government Publishing Service, Canberra.
9.
Standards Australia 1994, Australian Standard 1336-1994, Eye protection in
the Industrial Environment, Standards Association of Australia Publ., Sydney.
10.
Standards Australia/Standards New Zealand 1992, Australian/New Zealand
Standard 1337-1992, Eye Protectors for Industrial Applications, Standards
Association of Australia Publ., Sydney, Standards Association of New
Zealand Publ, Wellington.
11.
Standards Australia 1987, Australian Standard 2919-1987, Industrial Clothing,
Standards Association of Australian Publ., Sydney.
12.
Standards Australia 1990, Australian Standard 3765.1-1990, Clothing for
Protection against Hazardous Chemicals Part 1 Protection against General or
Specific Chemicals, Standards Association of Australia Publ., Sydney.
13.
Standards Australia 1978, Australian Standard 2161-1978, Industrial Safety
Gloves and Mittens (excluding electrical and medical gloves), Standards
Association of Australia Publ., Sydney.
FULL PUBLIC REPORT
11
14.
Standards Australia/Standards New Zealand 1994, Australian/New Zealand
Standard 2210-1994, Occupational Protective Footwear, Standards
Association of Australia Publ., Sydney, Standards Association of New
Zealand Publ, Wellington.
15.
National Occupational Health and Safety Commission 1994, National Code of
Practice for the Preparation of Material Safety Data Sheets
[NOHSC:2011(1994)], Australian Government Publishing Service, Canberra.
FULL PUBLIC REPORT
12
Attachment 1
The Draize Scale for evaluation of skin reactions is as follows:
Erythema Formation
Rating
Oedema Formation
Rating
No erythema
0
No oedema
0
Very slight erythema (barely
perceptible)
1
Very slight oedema (barely
perceptible)
1
Well-defined erythema
2
Slight oedema (edges of area welldefined by definite raising
2
Moderate to severe erythema
3
Moderate oedema (raised approx. 1
mm)
3
Severe erythema (beet redness)
4
Severe oedema (raised more than 1
mm and extending beyond area of
exposure)
4
The Draize scale for evaluation of eye reactions is as follows:
CORNEA
Opacity
Rating
Area of Cornea involved
Rating
No opacity
0 none
25% or less (not zero)
1
Diffuse area, details of iris clearly
visible
1 slight
25% to 50%
2
Easily visible translucent areas,
details of iris slightly obscure
2 mild
50% to 75%
3
Opalescent areas, no details of iris
visible, size of pupil barely
discernible
3
moderate
Greater than 75%
4
Opaque, iris invisible
4 severe
CONJUNCTIVAE
Redness
Rating
Chemosis
Rating
Discharge
Rating
Vessels normal
0 none
No swelling
0 none
No discharge
0 none
Vessels definitely
injected above normal
1
slight
Any swelling above
normal
1 slight
Any amount different
from normal
1 slight
More diffuse, deeper
crimson red with
individual vessels not
easily discernible
2 mod.
Obvious swelling
with partial eversion
of lids
2 mild
Discharge with
moistening of lids and
adjacent hairs
2 mod.
3
severe
Swelling with lids
half-closed
3 mod.
Diffuse beefy red
3
severe
Swelling with lids
half-closed to
completely closed
4
severe
Discharge with
moistening of lids and
hairs and
considerable area
around eye
IRIS
Values
Rating
Normal
0 none
Folds above normal, congestion, swelling, circumcorneal injection, iris reacts to light
1 slight
No reaction to light, haemorrhage, gross destruction
2 severe
FULL PUBLIC REPORT
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